EP1242353A1 - Procede de recuperation et de recyclage d'acide d-tartrique - Google Patents

Procede de recuperation et de recyclage d'acide d-tartrique

Info

Publication number
EP1242353A1
EP1242353A1 EP00991215A EP00991215A EP1242353A1 EP 1242353 A1 EP1242353 A1 EP 1242353A1 EP 00991215 A EP00991215 A EP 00991215A EP 00991215 A EP00991215 A EP 00991215A EP 1242353 A1 EP1242353 A1 EP 1242353A1
Authority
EP
European Patent Office
Prior art keywords
tartrate
acid
process according
tartaric acid
amino
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP00991215A
Other languages
German (de)
English (en)
Inventor
Kenneth Alfred Martin Kremer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP1242353A1 publication Critical patent/EP1242353A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/32—Separation; Purification; Stabilisation; Use of additives
    • C07C253/34—Separation; Purification
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/02—Preparation of carboxylic acids or their salts, halides or anhydrides from salts of carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/41—Preparation of salts of carboxylic acids
    • C07C51/412—Preparation of salts of carboxylic acids by conversion of the acids, their salts, esters or anhydrides with the same carboxylic acid part
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/42—Separation; Purification; Stabilisation; Use of additives
    • C07C51/43—Separation; Purification; Stabilisation; Use of additives by change of the physical state, e.g. crystallisation
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07B—GENERAL METHODS OF ORGANIC CHEMISTRY; APPARATUS THEREFOR
    • C07B2200/00—Indexing scheme relating to specific properties of organic compounds
    • C07B2200/07—Optical isomers

Definitions

  • the present invention provides a process for the recovery of es - sentially enantiomerically pure D-tartaric acid from a waste stream containing D-tartrate salts which comprises acidifying said waste stream to a pH of about 2.5 to 4.5 to obtain a crystalline alkali metal hydrogen D-tartrate; and reacting said alkali metal hydrogen D-tartrate. with an acid, optionally in the presence of a solvent.
  • the present invention also provides a process for the recycle of recovered D-tartaric acid in the continuous resolution of racemic 2-amino-2 , 3-dimethylbutyronitrile.
  • Imidazolinone compounds for instance, those described in U.S. 4,188,487, U.S. 4,798,619 and U.S. 5,334,576 are highly potent, broad spectrum, environmentally benign, herbicidal agents. In general, the herbicidal activity of the R-isomer is approximately 1.8 times that of the racemic imidazolinone compound.
  • Stereospe- cific processes to prepare chiral imidazolinone herbicidal agents, either directly or indirectly, from (R) 2-amino-2, 3 -dime- thylbutyronitrile are described in U.S. 4,683,324 and co-pending patent application Serial Number 09/304,401, filed an May 3, 1999.
  • Said nitrile is prepared by a two-step resolution of racemic 2 -amino-2 , 3-dimethylbutyronitrile using D- (-) tartaric acid as the resolving agent.
  • D-tartatic acid does not occur in abundance in nature, and methods for its production are limited.
  • D- tartaric acid is commercially available, it is expensive and is only available in limited quantities.
  • Imidazolinone compounds such as those described in U.S. 4,188,487, U.S. 4,798,619 and U.S. 5,334,576 are highly potent, broad spectrum, environmentally benign, herbicidal agents. Chiral imidazolinone compounds having the (R) configuration demonstrate an increase in herbicidal activity over the corresponding racemic mixture.
  • the two-step resolution described comprises a first resolution step in which racemic 2 -amino-2 , 3-dimethylbutyroni- trile (II) in C ⁇ C -alkanol is treated with D-tartaric acid (I) to afford the D-tartrate salt of (R) 2-amino-2 , 4-dimethylbutyroni- trile (III), which crystallizes from solution. Because said ami- nonitrile partially decomposes in the process of this kinetic resolution, the methanol mother liquor contains varying amounts of ammonium D-tartrate (IV) , which is ordinarily discarded.
  • This first resolution step is shown in Flow Diagram I wherein the C ⁇ -C -alkanol is methanol.
  • This second resolution step is illustrated in flow diagram II Q wherein M is an alkali metal and the water immiscible solvent is toluene.
  • D-tartaric acid is natural tartaric arid which occurs widely in nature, either as the free acid or in combination with potassium, calcium or magnesium
  • D-tartaric acid does not occur widely in nature and is commercially available only in limited quantities. Further, existing methods for producing D-tartaric acid are limited.
  • D-tartaric acid may be recovered in high yield and in essentially en- antiomerically pure form from the waste streams produced in the resolution of racemic 2-amino- 2, 3-dimethylbutyronitrile.
  • the recovered D-tartaric acid may be recycled for use in the same resolution of said aminonitrile.
  • the processes of this invention may be run repetitively, i.e., D-tartaric acid may be repeatedly recovered and recycled in a continu- ous resolution of racemic 2-amino-2 , 3-dimethylbutyronitrile, allowing for a sustainable resolution process.
  • the di (alkali metal) D-tartrate or ammonium D-tartrate waste streams produced in the resolution of the above-said aminonitrile are acidified to a pH of about 2.5 to 4.5, preferably 3.0 to 4.0, most preferably about 3.0.
  • the acidification is preferably conducted with hydro- chloric or sulfuric acid, to form the crystalline mono-basic hydrogen D-tartrate (VII) and said hydrogen D-tartrate is treated with at least one molar equivalent of an acid, optionally in the presence of a solvent, preferably an aliphatic alkanol, more pre- > ferably methanol or ethanol, to give essentially enantiomerically pure D-tartaric acid (I).
  • a solvent preferably an aliphatic alkanol, more pre- > ferably methanol or ethanol
  • the recovered D-tartaric acid (I) may then be utilized directly in the first resolution step by adding the recovered D-tartaric acid to a solution of racemic 2 -amino-2, 4-dimethylbutyronitrile in a water-immiscible solvent, such as toluene, to yield the corresponding D-tartrate salt (III) as shown hereinabove in flow diagram I .
  • Acids suitable for use in the process of the invention include mineral acids such as hydrogen halides, sulfuric acid, phosphoric acid, or the like, preferably hydrochloric acid or sulfuric acid.
  • Solvents suitable for use in the inventive process include polar solvents, preferably water miscible.
  • Preferable solvents include aliphatic alkanols such as methanol, ethanol, propanol, isopropa- nol, or the like, preferably methanol or ethanol, more preferably ethanol .
  • Alkali metals include sodium, potassium, or lithium, preferably sodium or postassium.
  • reaction temperatures for the inventive process are directly related to reaction rate, that is increased reaction temperature leads to increased, reaction rate.
  • exces- sively high reaction temperatures are to be avoided.
  • Suitable reaction temperatures may be about 0°C to 50°C, preferably about 5°C to 35°C, more preferably about 10°C to 30°C.
  • waste streams from a 2-step resolution of racemic 2-amino-2 , 3-dimethylbutyronitrile, combined or individually, are acidified to a pH of about 3 to form crystalline alkali metal hydrogen D-tartrate and said hydrogen D-tartrate is reacted with at least one molar equivalent of acid, preferably hydrochloric acid or sulfuric acid, optionally in the presence of a sol- vent, preferably an aliphatic alkanol, more preferably methanol or ethanol, to give the desired essentially enantiomerically pure D-tartaric acid.
  • acid preferably hydrochloric acid or sulfuric acid
  • the crystalline alkali metal hydrogen D-tartrate may be isolated using conventional means such as filtration or, alternatively, may be carried on in the inven- tive process as is or as a concentrated slurry.
  • the recovered D-tartaric acid may be isolated using conventional techniques or recycled as is or as a concentrated slurry.
  • HPLC designates high performance liquid chromatography. Unless otherwise indicated, all parts are parts by weight.
  • a mixture of aqueous disodium tartrate waste produced as described in Example 1 (438.5 g, 14.5 wt% D-tartaric acid) and a methanolic mother liqucr waste slurry of ammonium tartrate (278 g, 2.6 wt% D-tartaric acid) produced as described in U.S. 4,683,324 is acidified to a pH of about 3 with concentrated hydrochloric acid over a 30 minute period at room temperature, stirred for 25 minutes and filtered. The filtercake is washed with methanol and dried under reduced pressure to afford 73.7 g (92% recovery) of D-sodium hydrogen tartrate as an off-white solid, in >99% purity and 100% optical purity, as determined by HPLC analysis.
  • a slurry of recovered D-sodium hydrogen tartrate (20.6 g, 0.119 mol) in methanol is treated with concentrated sulfuric acid (6.1 g, 0.059 mol) at room temperature, stirred for one hour and filtered to remove inorganic salts. A portion of the filtrate is concentrated under reduced pressure to give a solution of recovered D-tartaric acid (13.6 g, 0.090 mol, 82%) in methanol. This solution is treated with a solution of racemic 2-amino-2, 3-dimethylbutyronitrile (12.4 g, 0.11 mol) in toluene, stirred for 16 hours and filtered.
  • Aqueous dipotassium tartrate waste (137.0 g, 14.7 wt% D-tartaric acid) is acidified to a pH of about 3 with concentrated hydrochloric acid over a 30 minute period at 13-28°C, stirred for about 15 minutes and filtered.
  • the filtercake is washed with methanol and dried under reduced pressure to afford 24.8 g (98% recovery) of D-potassium hydrogen tartrate, in >99% purity, as determined by HPLC analysis.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

Abstract

L'invention porte sur un procédé de récupération d'acide D-tartrique, fait essentiellement d'énantiomères purs, à partir de flux de déchets aqueux et organiques par dédoublement du 2-amino-2,3-diméthylbutyronitrile racémique via la formation et l'isolement d'un tartrate monobasique cristallin. L'acide D-tartrique optiquement pur ainsi récupéré peut être recyclé efficacement pour permettre le dédoublement en continu du 2-amino-2,3-diméthylbutyronitrile racémique.
EP00991215A 1999-12-28 2000-12-19 Procede de recuperation et de recyclage d'acide d-tartrique Withdrawn EP1242353A1 (fr)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
US17337299P 1999-12-28 1999-12-28
US173372P 1999-12-28
US47364899A 1999-12-29 1999-12-29
US473648 1999-12-29
PCT/EP2000/012946 WO2001047856A1 (fr) 1999-12-28 2000-12-19 Procede de recuperation et de recyclage d'acide d-tartrique

Publications (1)

Publication Number Publication Date
EP1242353A1 true EP1242353A1 (fr) 2002-09-25

Family

ID=26869068

Family Applications (1)

Application Number Title Priority Date Filing Date
EP00991215A Withdrawn EP1242353A1 (fr) 1999-12-28 2000-12-19 Procede de recuperation et de recyclage d'acide d-tartrique

Country Status (7)

Country Link
EP (1) EP1242353A1 (fr)
CN (1) CN1414939A (fr)
AR (1) AR027145A1 (fr)
AU (1) AU3160601A (fr)
BR (1) BR0016803A (fr)
IL (1) IL150155A0 (fr)
WO (1) WO2001047856A1 (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN101643409B (zh) * 2009-08-31 2013-04-24 厦门世达膜科技有限公司 一种将酒石酸钠转化成酒石酸的生产方法
CN101782548B (zh) * 2009-12-03 2013-07-24 浙江工业大学 一种毛细管电泳拆分2,4-滴丙酸对映体的新方法
CN101906032A (zh) * 2010-07-14 2010-12-08 华东理工大学 回收和循环使用l-(+)-酒石酸的方法
CN102503810B (zh) * 2011-11-02 2014-05-21 浙江科技学院 一种回收和循环使用l-酒石酸的方法
CN103834964A (zh) * 2013-12-31 2014-06-04 浙江工业大学 一种毛细管电泳拆分2-甲基-4-氯戊氧基丙酸对映体的方法
CN105152911B (zh) * 2015-08-17 2017-05-31 浙江邦成化工有限公司 一种酒石酸的回收方法
MD4504C1 (ro) * 2016-04-13 2018-03-31 Общественное Учреждение "Научно-Практический Институт Садоводства И Пищевых Технологий" Procedeu de obţinere a acidului tartric din tartratul de calciu obţinut din deşeuri vinicole

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE264005C (fr) *
US4683324A (en) * 1982-05-25 1987-07-28 American Cyanamid Company Process for the resolution of certain racemic amino nitriles
DE19819884A1 (de) * 1998-05-04 1999-11-11 Metallgesellschaft Ag Verfahren zum Erzeugen von Weinsäure aus einem Kaliumhydrogentartrat enthaltenden Rohmaterial

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0147856A1 *

Also Published As

Publication number Publication date
IL150155A0 (en) 2002-12-01
AR027145A1 (es) 2003-03-12
AU3160601A (en) 2001-07-09
WO2001047856A1 (fr) 2001-07-05
BR0016803A (pt) 2002-09-10
CN1414939A (zh) 2003-04-30

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